Azo dyestuffs and process for the manufacture of same



Patented May 1, 1923.

UNETED STATES PATENT GFFHQE.

GUILLAUME DE MONTMOLLIN, GERALD BONHGTE, AND JOSEF SPIELER, OF BASEL, SWITZERLAND, ASSIGNORS TO SOCIETY OF CHEMICAL INDUSTRY IN BASLE, OF

BASEL, SWITZERLAND.

AZO DYESTUFFS AND PROCESS FOR THE, MANUFACTURE OF SAME.

No Drawing.

To all whom, it may concern:

. Be it known that we, GUILLAUME m: MoNTMoLLIN, GERALD Boxrrorn, and Josnr SPInLEmall citizens of the Swiss Republic,

.and residents of Basel, Switzerland,have invented new and useful Azo Dyestuffs and Processes for the Manufacture of Same, of which the following is a full, clear, and exact specification.

This invention relates to the manufacture of dyestuffs which are technically of great value by coupling with a diazo-compound (in certain cases with elimination of l or 2 molecular proportions of carbon dioxide) 1' 0r 2 carbonyl derivatives derived from 1-0xynaphthalene-a-carboxylic acid andv of the general formula 561920,- filed May 18th, 1922, and in another U. S. patent application. recently filed, the

' arylides of 1-oxynaphthalene-4-carboirylic acid which can be prepared by the action of an aromatic amine on one of the ethereal salts of l-oxynaphthalene-4-carboxylic acid named in the original U. S. patent applica= tion Serial No. 561920, filed May 18th, 1922. or a et-oxynaphthalene-1-arylketone, or a carboxylic acid derivative thereof capable of bein obtained by the processes described in the S. patent application Serial No. 575- 579, filed July 17th, 1922, and in another U.

S. patent application, recently filed. The new dyestuffs thus obtained, which constitute orange to blue and brownish black powders soluble to insoluble in water and producing on the material to which they are ap- Application filed February 6, 1923.

Serial No. 617,385.

plied orange to violet blue and brownish black tints, correspond with the general formula wherein n signifies a whole number smaller than 3, R any armomatic complex which may contain substituents, and R the radical of the already mentioned carbonyl derivative derived from the l-oxynaphthalenelcarboxylic acid which may also contain other substituents. According to the nature of the diazo-compound used, an acid dyestuif may be produced suitable for wool, or a dyestuff suit-able for the manufacture of pigments and lakes, or a dyestufl formed on the fiber in the same manner as paranitraniline red is produced. In this latter case particularly remarkable results are obtained by employin unsulfonated diazo-compounds correspon ing' with the general formula A{/N=NOH} i in which n is a whole number smaller than 3, A an aromatic complex which may contain substituents, and X agroup OR (in which R is an alkyl, aryl and aralkyl radical) in ortho-position to -the diazogroup. Generally speaking, the dyestuffs or the dyeings produced by them are distinguished by their vividness, their intensity and their fastness.

The following examples illustrate the in- I vention without limiting it, the parts being by weight E rample pound mentioned one which is obtained from a sulfonated derivative of toluidine, a scarlet dyestuif may be obtained.

Ewample 2.

86 parts of metanilic acid are diazotized in the usual manner and the diazo-compound produced is added to a mixture of 1000 parts of ice, 196 parts of 4-oxynaphthalene l phenylketone 3-carboxylic acid and 100 parts of anhydrous sodium carbonate. Coupling occurs rapidly with elimination of a molecular proportion of carbon dioxide; the dyestuif is isolated as indicated in Example 1. It dyes wool in an acid bath orange red. When precipitated with a salt of barium it yields red lakes of excellent fastness to water, oil and light.

The same dyestuif is obtained if 4-oxynaphthalene-l-phenylketone be substituted for the 4-oxy-naphthalene-l-phenylketone- 3-carboxylic acid. These ketones combine with diaZo-compounds of the naphthalene series, such as Q-naphthylamine-l-(or 6-) sulfonic acid, to yield dyestuffs which give with suitable mineral salts blood red lakes and dye wool vivid red tints fast to washing.

E wample 3.

E mample 4.

Cotton is prepared in the usual manner with an alkaline solution containing per litre 20 grams of tzt dioxy-l zl dinaphthylketone and is then passed through a bath containing per litre 10.7 grams of diazotized orthotoluidine. The cotton is dyed anintense red; the tint is fast to washing and to light.

Ewa-mple 5.

Cotton is prepared in the usual manner with an alkaline solution containing per litre 30 grams of the anilide of l-ox-ynaphthalene-et-carboxylic acid and is then passed through a bath containing per litre 22.5 grams of ortho-amino-azo-toluene which has been diazotized. The cotton is dyed an intense bordeaux tint, fast to light, washingand chlorine.

Example 6.

The fabric to be printed is padded with an alkaline bath containing per litre 15.5 gr. of 4:4-dioxy-l:1dinaphthylketone and is then printed in the usual manner with a printing paste containing per litre 15.8 grams of 5-nitro-2-amino-l-inethoxybenzene which has been diazotized. The dark bluish red color is developed immediately and is very fast. By soaping the not printed portions are made white. The same result is obtained by impregnating the fiber with the corresponding quantity of the 4,4-dioxy-1.l' -dinaphth vlketone 3,3-dicarboxylic acid.

The following table indicates tints which may be obtained by dyestuffs made in accordance with the invention.

Carbonyl derivative. Base dlazotized. Tint.

4:4 dioxydinanhthyl Anisidinesulfonic acid Blood red.

ylic acid or 4:4-diox- H24).

ydinaphthyletone.

Do Ortho toluldine sul Scarlet.

ionic acid (CHM, NH fiQ, S03E14).

Do Para-toluidinesnlfonlc Scarlet.

acid (CHgIl, NH2:4,

D 1???) Do ianis d ne Brow'nish bl D0 Ortho-toluldine. Red. ck 4 oxynaphthalene 1 Metanilic acid Red.

phenyl-ketone-B-carboxylic acid and 4- oxynaphthalene 1 phenylketone.

Do Sulfanillc acid Red.

Do Nanhthionic acid Violet red.

(NH rl, some Do Nanhthionic acid Red.

(NH z2, S0 E11).

Do Naphthlonic acid Red.

Do Param't raniline Orange red.

D Chlor0-anisidine (C124, Vivid red.

Do Nitro ortho toluidlne Vivid red.

(NOQA, CH rl, NHg:

Do Nitro-anisidlne (N0 Red.

5, OCH 11, Nina).

Para-chloraniline Orange red. Dlchloraniline Orange red. ornaphthylamlne." Garnet. Chloro B naphth Red.

' amine (01:1, NH :2).

Do Phenyl ether of 4 Scarlet.

chloro 2 amino 1 phen Do Para-cresyl-ether of 4- Scarlet. chloro-2-amino-1 phenol.

Do Benzyl ether of 4 Blood red.

q ch1oro-2-amino-lphenol.

Do 4 chlorophenyl other Scarlet orange.

' of 4-chloro-2-amlno l-phenol.

Do 4-chloro-3-cresyl-etha' Scarlet.

of 4-chloro-2-aminol-phenol.

Do Phenyl ether 0! 2-am1- Red.

- nod-phenol- Carbonyl derivative. Base diazotized. Tint.

Do Benzylether of S-ami- Violet red.

no-l-methylphenol. Do Phenyl ether of i-ethyl- Scarlet orange.

i sulfon 2 amino l phenol. Benzidine i Puce. Dianisidine Very violet blue. 4:4 diaminodlphenyl- Brownish black.

amine. Diaminodiphenyl-ether -led. Ortho amino azo -tol- Garnet.

. uene. 4 oxynaphthalene -1 Chloro S naphthyl- Red.

(2 chloro) phenylamine (Cl:l,NH- :2). ketone 3 carboxylic acid and 4-oxynaphthalene- 1 -('2'-chloro)- phenylketone.

Do Benzyl ether uf i-ethyl- Blood red.

sulfon 2 aminophe nol. Dianisidine Very violet blue.

Do 4 oxynaphthalene 1- (4'-cholro) phenylketone-3-carboxylic acid and 4-oxynaphthalene-l- (4' chloro) phenylketone. 4- oxynaphthulene 1 .do

(2-i dichloro) phel nyllzetone 3 carboxylic acid and 4oxynaphthalenel (2'4- chloro)- phenylketone l chloro- 2:1 dinaphthylketone 4 oxy- 3-carboxylic acid and 1 chluro 4' oxy-2:1- dulsaphthylketone.

Phenyl ether of 4-chlo- Scarlet.

ro- 2-aminol -phenol.

Phenyl ether of i-chloro-Q-aminwhphenol.

Blood red.

Benzyl ether of -l-chloro-Z-arnino-i-phenol. Dianisidine i Phenyl ether of 4-chlo- 'ro-Z-aminol-phenol.

Blood red.

Very violet blue. Scarlet Do Anilide OI l-oxynaphthalene 4 carboxylic acid. Para-toluidide of l-oxy- .dO Do. naphthalene-Learboxyhc acid. Methylanilide of l-oxy- .do Do.

naphthalene--carboxylic acid.

What we claim is: 1. The herein described manufacture of new azo-dyestufi's by combining carbonyl derivatives derived from l-oxynaphthalene-etcarboxylic acid and of the general formula wherein R signifies a complex which consists in at least one aromatic nucleus, with unsulfonated diam-compounds.

I). The herein described production of new dyestuffs on the fiber by treating the fiber first with unsulfonated carbonyl derivatives derived from 1-oxynaphthalene-4- carboxylic acid and of the general formula wherein R signifies a complex which consists in at least one aromatic nucleus, and then with unsulfonated diaZo-componnds.

at. The herein described manufacture of new azo-dyestufis by combining unsulfonat ed eoxynaphthalene-l-arylketones with unsulfonated diaZo-coinpounds.

5. The herein described production of new dyestuffs on the fiber by treating the fiber first with unsulfonated -oxynapththalene I-aryllretones and then with unsult'onate-d diam-compounds.

6. The herein described production of new d t'estufis on the fiber by treating the fiber first with unsulfonated and uncarboxylated 1-oxynaphthalene-l-arylketones and then with unsulfonated diazo-compounds.

7. The herein described production of new dyestuffs on the fiber by treating the fiber first with unsulfonated and uncarbo'xylated l-oxynaphthalene-l-arylketones and then sponding with the general formula wherein n signifies awhole number smaller than A an aromatic complex which may contain substituents, and X a group()R (wherein R represents an alkyl, aryl, and aralkyl radical) in ortho position to the diam-group.

8. The herein described production of new dyestuffs on the fiber by treating the fiber first with unsulfonated and uncarboxylated l-oxynaphthalene-l-arylketones and then with unsulfonatcd diam-compounds corresponding with the general formula .(R \'=X),.R

wherein n signifies a whole number smaller than 3, R any aromatic complex which may contain substit-uents, and R the radical of a carbonyl derivative derived from l-oxynaphthalene-4-carboxylic acid and of the general formula on COR wherein R signifies a complex which consists in at least one aromatic nucleus, which dyestuffs constitute orange to blue and brownish black powders soluble to insoluble in water, producing on the material to which they are applied orange to violet blue and brownish black tints.

10. The herein described new dyestuffs re-- sulting from the action of unsulfonated diazo-compounds on the carbonyl derivatives derived from 1 oxynaphthalene-t-carboxyl c acid corresponding with the general formula (R' N=N- .,R n wherein n signifies a whole number smaller than 3, R an unsulf'onated aromatic complex which may contain other substituents, and R the radical of a carbonyl derivative derived from 1-oxynaphthalene-4-carboxylic acid and of the general formula WOW-R wherein R signifies a complex which consists in at least one aromatic nucleus, which dyestuffs constitute orange to blue and brownish black powders insoluble in water, producing on the fiber to which they are applied orange to blue and brownish black tints. 11. The herein described new dyestuffs resulting from the action of unsulfonated diazo-compounds on the unsulfonated derivatives of 4-oxynaphthalene-l-arylketones corresponding with the general formula (RN=N)nR wherein /L signifies a .whole number smaller than 3, R an unsulfonated aromatic complex which may contain other substituents, and.

R the radical of an unsultonated 4-oxynaphthalene-l-arylketone, which dyestuffs constitute orange to blue and brownish black powders insoluble in water, producing on the fiber to which they are applied orange to blue and brownish black tints.

12.The herein described new dyestuffs resulting from the action of unsulfonated diazo-compounds on the unsulfonated derivatives of the 4-oxynaphthalene-l-arylketones corresponding with the general formula wherein n signifies a whole number smaller than 3, R an unsulfonated aromatic complex wherein R signifies an unsulfonated aromatic complex comprising, besides other eventual substituents, a group ()R (wherein B may represent an alkyl, aryl and aralkyl radical) in ortho-position to the azogroups, and R the radical of an unsulfonated 4-oxynaphthalene:l-arylketone, which dyestuffs constitute orange to brownish-violet red powders, producing on the fiber to which they are applied orange to blue red tints.

14:. Materials dyed with the new azo-dyestuflsresulting from the action of unsulfonated diazo-compounds on the carbonyl derivatives derived from l-oxynaph'thalenelcarboxylic acid corresponding with the general formula wherein n signifies a whole number smaller than 3, R an unsulfonated aromatic complex which may contain other substituents, and R theradical of a carbonyl derivative derived from 1-oxynaphthalene-4-carboxylic acid and of the general formula wherein R signifies a complex which consists in at least one aromatic nucleus, the dyes being of orange to blue and brownish black tin 15. Materials dyed with the new azo-dyestuffs resulting from the action of unsulfollO nated diazo-compounds on the unsulfonated derivatives of t-oxynaphthalene-l-arylketonles corresponding with the general formu a wherein n signifies a whole number smaller than 3, R an unsulfonated aromatic complex which may contain other substituents, and R the radical of an unsulfona'ted it-oxynaphthalene-l-alylketone, the dyes being of orange to blue and brownish black tints wherein n signifies a whole number smaller than 3, R an unsulfonated aromatic complex comprising, besides other eventual substituents, a group -OR (wherein R may represent an alkyl, aryl, and ara'lkyl radical) in ortho-position to the azo-groups, and R the radical of .an unsulfonated -oxynaphthalene-l-arylketone. the dyes being of orange to violet blue tints.

17. Materials dyed with the new azo-dyestufi's resulting fromthe action of unsulfonated diazo-compounds on the unsulfonated derivatives of the 4-oXynaphthaiene-1-arylketones corresponding with the general forwherein R signifies an unsulfonated aromatic complex comprising, besides other eventual substituents. a group OR (wherein B may represent an alkyl, aryl and aralkyl radical) in ortho-position to the azogroups. and'R the radical of an unsulfonated l-oxynaphthalene-l-arylketone, the dyes being of orange toblue red tints. I

In witness whereof we have hereunto Signed our names this th day of J anuary;

19 23, in the presence of two subscribing wit- IIESSQS.

GUILLAUME m: MONlMOLLIN. GERALD BONHOTE. JOSEF SPIELER. \Vitnesses ARMAND GRAUN, MABGUERITE STAEHELI. 

